Compound of the diphenyl methane series and process of preparing the same



patented July 4, 1933 teal- UNITED STATES PATENT Fr es IVAN GUBELMANNHENRY J. WEILAND VVAUKEE, WISGON SIN, ASSIGNORS, BY

COMPOUND OF THE DIPI-IENYL-METHANE SERIES AND OTTO STALLMANN, OF SOUTH MIL- MESNE ASSIGNMENTS, TO E. I. DU PONT DE. NELIOURS &. COMPANY, A CORPORATION OF DELAWARE AND PROCESS OF PREPARING THE SAIME N0 Drawing.

This invention relates to amino benzyl paring the same. It also relates to the nitrogen substitution products of the same, as for example, where the substituted groups are acidyls; acetyl, benzoyl, and phthaloyl, or derivatives of urea and the like. It includes in general those amino bodies which are prepared from benzoyl ortho benzoic ac1ds by the steps of nitrating, reducing the nitro body to the amino group and then reducing the GO group to a CH group. This invention does not include the il-aminobenzyl benzoic acid derivatives, as these are a subject of a copending application.

It is an obj cct of this invention to provide a method whereby these products may be made technically available for use as such, since they are valuable products of themselves and more particularly so when used as the starting material for the preparation of dyestuifs.

Other and further important objects of this invention will become apparent from the following description and appended claims.

We have found that the amino benzyl ortho benzoic acids may be prepared by reducing the corresponding benzoyl ortho ben zoic acids by methods adapted forreducing similar bodies, as for example, by the use of ammonia and zinc dust. The'N-substituted derivatives may be prepared from the benzyl benzoic acids by known methods of preparing these derivatives from other aniline bodies. These ll-substituted derivat1ves can also be prepared by first making the benzoyl benzoic acid derivative, then reducmg this with ammonia and zinc to the benzyl derivative. The acidyl amino benzyl ortho benzoic acid can be hydrolyzed back to the amino benzyl ortho benzoic acid by known methods applicable to analogous compounds. The following equation expresses the most probable reaction taking place in reducing the amino benzoyl ortho benzoic acids to the amino benzyl ortho benzoic acids.

CO2H 002B in which (R) represents a benzene nucleus Application. filed July e, 1328. Serial No. 290,027.

with a hydrogen in the (2) or (3') position I substituted with an amino group or a substituted amino group like acetyl amino, benzoyl amino, toluene-sultonyl amido, phthaloylamidoand the like. The hydrogen in the etposition may be substituted by such groups as methyl, chloro, carboXy and the like.

Amongthe amino bodies which we have prepared are the following: 3amino-benzyl ortho benzoic acid, 8-amino-4 chloro-ben zyl ortho benzoic acid, 3-a1nino-l-methyl benzyl ortho benzoic acid, 3-amino-4-carboXy-benzyl ortho benzoic acid, and a mixture of 2-amino and 3 amino-benzyl ortho benzoic acid as prepared by nitrating and reducing ortho benzoyl benzoic acid and then subsequently reducing the CO group to -The amino benzyl benzoic acids contemplated by this invention are white to cream colored solids depending upon the purity of the product. They are in generalsoluble in concentrated ammonia. are dissolved 275 parts of 3'amino-4 chloro-benzoyl ortho benzoic acid. A solution of parts of copper sulfate crystalsin 300 parts of water is then added. There are'then added 500 parts of zinc dust and the mass is well agitated, the

In 1500 parts of water-and 1000 parts of temperature of the solution being held at to (1, for about 7 hours. The zincresidues are removed by filtrationand to the filtrate is added suilicient sodium carbonate to completely decompose the ammonium salts. The ammonia is then distilled off. The resid ual solution is then filtered from further salt residues and precipitated by the use of acid until a maximum precipitation of 3-amino- 4-chloro benzyl ortho benzoic acid occurs. After stirring cold for a while the product is filtered ofi. It can be recrystallized from benzene in the form of white crystals having a melting point of 132 C.

Other amino benzoyl ortho benzoic acids which is a member of the group consisting may be treated in a similar manner to give of primary 3-ammo-benzyl-orthohcnzoic the corresponding ammo benzyl ortho benacid and the N-substituted 3-ammo-benzylzoic acids. ortho-benzoic acids in which the N-substitu- 5 The acidyl derivatives or the urea derivaout is an acidyl group or a urea radical.

lives may be made according to known meth- 4. 3-amino benzyl ortho benzoic acids. ods of reacting upon an amine to form the 5. Amino-henzyl-ortho-henzoic acids in corresponding acidyl or urea derivatives. As which the amino group is located in the benan example, for the preparation of the 3- zene nucleus in a position other than para to acetylaminol-chloro-benzoyl benzoic acid the CH: group. 7 We give the following by way of illustre i n. 6. 3" amino benzytortho henzoic acids The amino body is added to glacial acetic having most probably thefollowingconstituacid and to this solution is added some acetic tion: l anhydride and the mixture heated for a short a time. After cooling and diluting with water 1 R] the acetyl derivative separates in the form of white crystals. Upon recrystallizing from acetic acid, the melting point of the purified product is 215 to 216 C.

Some. of the acidyl amino derivatives oi: E $5 the benzyl ortho benzoic acids may be pre pared from the corresponding acldyl ammo benzo '1 benzoic acids by treating the acidyl amino benzoyl benzoic acid in a slmilar manncr as is done with the unsubstituted amino 1 a i 1 I bemovl acid This is particularly wherein in anc llrepresent tuo iyorogca WW; .J' the case with those N-substituted bodies i-i h F2 1 f 1 which not Q0 easily hvdmlyyed as for cal or a divalent aciuyl radical and R rcp- V I ..ii..',i. example the phthaloyl ammo bodles lesengs a ii) 0.1 ogen atom, a LiliOrlllu atom or r t \Ve are aware that numerous details of 3 11 r :1 P the process may be varied through a wide 3 1 f mnfle without d'epartino, m the Principles which are members or the group consisting a '2 rT 'A of this invention, and We, therefore, do not p t 011.110 bmwu purpose hmitino the patent granted hereon acid and the A -substituted a -amino-benzyl Otherwise than Eecessitated by the Prior art. ortho-benzzoic acids in which the N-suostit- We claim as our invention:

uent is an acidyi group or a urea radical.

1. The process of preparing a 3'-amino- -COOH 8. 3-amino-benzyl ortho benzoic acids benzyl ortho benzoic acid which is a member substituted in the y-POSL G'LOII by an alkyl, of the group consisting of primary 3-amino- 952 ycarboxy F P' V 4o benzyl-ortho-benzoic acid and the N-substi- P o Q pw jl 3 3 tuted h ic acids in henzyl-ortho-benzoic acid which is a mem- 3 1 z' l which the N-subst1tuent1s an acidyl group or Gimme 1 n i g P fy 5 a urearadical, which comprises reducing the 311111119benzyLolthQ'benzolc f flindjtne N- corresponding 3' i b l th b substituted 3 amino benzyl-orthopenzorc i id acids inwhich the ll -subst1tueut is an acidyl 2 T118 process of preparing' a 3 be Y1 group 01 (1 HIGH, radical. \Vlllflil COmPIISOS leth b i id whi h i a be f th ducingthe correspondlng 3-aniino-benzoylgroup consisting of primary 3'-amino-b loi'tho-beuZorc acid with zinc n an ammoniaorthobenzoic acid and the N b tit t d 3 cal solution 111 18 presence or copper sulfate amino-benzyl-ortho-benzoie id i hi h at temperature of between and C.

th N-gubst tuent- 15 a d l group or a in testimony whereof we have hereunto urea radical, which comprises reducing th subscribed our names at Carrollville, Milcorrespondmg 3-,am1no-benzoyl-ortho-ben- Waiiliee County, Wis.

zoic acid with zinc in an ammoniacal solu- IVAN GUBELMANN.

5.; tion in the presence of copper sulfate. EENRY J. \VEILAND 1 3. A 3-amino-benzyl-ortho-benzoic acid ()lTO STALLMANN. 

